Alkoxyimino phosphinates

ABSTRACT

COMPOUNDS OF THE FORMULA   Y1-P(-X1)(-Y2)-X2-CH(-Q)-C(-O-R1)=N-O-R2   WHEREIN Y1 AND Y2 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL AND   ZM-PHENYLENE-(CH2)N-   WHEREIN Z IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, HALOGEN, NITRO, DIALKYLAMINO, ALKYLSULFOXIDE AND ALKYLSULFONE, M IS AN INTEGER FROM 0 TO 5, AND N IS AN INTEGER FROM 0 TO 3; Q IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO AND   BP-PHENYLENE-(A)Q-   WHEREIN B IS SELECTED FROM THE GROUP CONSISITING OF ALKYL, ALKENYL, ALKOXY, ALKYLTHIO, HALOGEN, NITRO, DIALKYLAMINO, ALKYLSULFOXIDE AND ALKYLSULFONE, P IS AN INTEGER FROM 0 TO 5, A IS SELECTED FROM THE GROUP CONSISTING OF OXYGEN, SULFUR, ALKYLENE, ALKYLENEOXY AND ALKYLENETHIO, AND Q IS AN INTEGER FROM 0 TO 1; X1 AND X2 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF OXYGEN AND SULFUR; AND R1 AND R2 ARE ALKYL. THIS INVENTION ALSO DISCLOSES INSECTICIDAL AND ACARICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND, AS AN ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITY TOXIC TO INSECTS AND ACARIDS, A COMPOUND OF THE ABOVE DESCRIPTION; AND FURTHER, A METHOD OF DESTROYING INSECTS AND ACARIDS WHICH COMPRISES APPLYING TO SAID INSECTS AND ACARIDS AN A FORESDESCRIBED INSECTICIDAL AND ACARICIDAL COMPOSITION.

United States Patent 3,597,508 ALlKUXYlMINO PHOSPHINATES Sidney B.Richter, Skokie, and Ephraim H. Kaplan,

Chicago, llL, assignors to Velsicol tChemical @orporation, Chicago, 111.No Drawing. Filed Oct. 7, 1968, Ser. No. 765,617 lint. Cl. (307i 9/32;Atlln 9/36 US. Cl. 26tl-944 6 Claims ABSTRACT 9F THE DIESCLGSURECompounds of the formula wherein Y and Y are independently selected fromthe group consisting of alkyl, alkenyl and rs-m) wherein Z is selectedfrom the group consisting of alkyl, alkenyl, alkoxy, alkylthio, halogen,nitro, dialkylamino, alkylsulfoxide and alkylsulfone, m is an integerfrom to 5, and n is an integer from 0 to 3; Q is selected from the groupconsisting of alkyl, alkenyl, alkoxy, alkylthio and wherein B isselected from the group consisting of alkyl, alkenyl, alkoxy, alkylthio,halogen, nitro, dialkylamino, alkylsulfoxide and alkylsulfone, p is aninteger from 0 to 5, A is selected from the group consisting of oxygen,sulfur, alkylene, alkyleneoxy and alkylenethio, and q is an integer from0 to l; X and X are independently selected from the group consisting ofoxygen and sulfur; and R and R are alkyl. This invention also disclosesinsecticidal and acaricidal compositions comprising an inert carrierand, as an essential active ingredient, in a quantity toxic to insectsand acarids, a compound of the above description; and further, a methodof destroying insects and acarids which comprises applying to saidinsects and acarids an aforedescribed insecticidal and acaricidalcomposition.

This invention relates to new chemical compositions of matter, and moreparticularly relates to new compounds of the formula wherein Y and Y areindependently selected from the group consisting of alkyl, alkenyl and H(5-rn) wherein Z is selected from the group consisting of alkyl,alkenyl, alkoxy, alkylthio, halogen, nitro, dialkylamino, alkylsulfoxideand alkylsulfone, m is an integer from O to 5, and n is an integer from0 to 3; Q is selected from the group consisting of alkyl, alkenyl,alkoxy, alkylthio and 3,597,508 1c Patented Aug- 9 1971 H s-m) wherein Zis selected from the group consisting of lower alkyl, lower alkenyl,lower alkoxy, lower alkylthio, chlorine, bromine, nitro, di(loweralkyl)amino, lower alkylsulfoxide and lower alkylsulfone, and m and nare integers from O to 3; Q is selected from the group consisting oflower alkyl, lower alkenvl, lower alkoxv, lower alkvlthio and tS-n)wherein B is selected from the group consisting of lower alkyl, loweralkenyl, lower alkoxy, lower alkylthio, chlorine, bromine, nitro,di(lower alkyl)arnino, lower alkylsulfoxide and lower alkylsulfone, p isan integer from 0 to 3, A is selected from the group consisting ofoxygen, sulfur and alkylene, and q is an integer from 0 to 1; X and Xare selected from the group consisting of oxygen and sulfur; and R and Rare lower alkyl. The term lower as used herein designates a branched orstraight carbon chain of up to about ten carbon atoms.

The compounds of the present invention are unexpectedly useful aspesticides, particularly as insecticides and acaricides.

The alkali metal phosphinates of Formula III which pared from compoundsof the formula wherein Hal designates halogen, preferably chlorine orbromine, and Q, R and R are as hereinabove described, by reaction withabout an equimolar amount of an alkali metal phosphinate of the formulaX1 Y X M Y2 (III) wherein M is an alkali metal and Y Y X and X are asheretofore described. This reaction can be effected by heating thereactants in an inert organic solvent such as methyl ethyliketone at thereflux temperature of the reaction mixture for a period of from about 4to about 24 hours. After the reaction is completed the reaction mixturecan be filtered to removed the alkali metal halide which has formed. Thedesired product can then be conveniently recovered as a residue uponevaporation of the solvent from the remaining solution. The product canbe used as such or can be further purified by washing, distillation orchromatography if the product is an oil, or by trituration,recrystallization or other common methods well known in the art if theproduct is a solid.

The compounds of Formula II can be prepared from an N-alkoxy amide ofthe formula (HaD-CfH-ii-ITI-OR Q H (IV) wherein Hal stands for halogensuch as chlorine or bromine and Q and R are as hereinabove described, byreaction with a diazoalkane. This reaction can be eifected by slowlyadding a solution of the amide of Formula IV, with stirring, to a slightmolar excess of a solution of the diazoalkane at a temperature belowabout 15 C. and preferably at a temperature of from about to about 10 C.Suitable solvents for the reactants are inert organic solvents such asether, benzene or ether-ethanol mixtures and the like. After theaddition is completed, stirring can be continued for a short period toinsure completion of the reaction. The desired product can then berecovered by evaporation of the solvents used and can be used as such orcan be further purified by conventional techniques well known in theart.

Exemplary diazoalkanes suitable for reaction with the alkoxyacetamidesof Formula IV to form the compounds of Formula II are diazomethane,diazoethane, diazo-npropane, diazo-n-butane, diazoisobutane,diazo-n-pentane, diazo-n-hexane, diazo-n-octane, and the like.

Exemplary suitable compounds of Formula IV for the purpose of preparingthe compounds of Formula II are:

N-methoxy-a-chloropropionamide N-methoxy-a-chloro-n-butyramideN-ethoxy-a-chloroisobutyramide N-methoxy-u-chloro-n-valeramideN-isopropoxy-u-chloro-n-caproamide N-methoxy-a-phenyl-a-chloroacetamideN-methoxy-a- 4-chlorophenyl) -a-chloroacetamide N-methoxy-a-(Z-methylphenyl) -a-chloroacetamide N-methoxy-zx- 3-nitrophenyl-a-chloroacetamide N-ethoxy-a-(3-dimethylaminophenyl)-a-chloroacetamideN-methoxy-a-(2,6-dimethoxy-4-chlorophenyl)flit-chloroacetamideN-methoxy-a-benzyl-ot-chloroacetamideN-pentoxy-a-(3-chlorobenzyl)-a-chloroacetamideN-ethoxy-a-(2-methoxyphenyl)-a-chloroacetamide The alkali metalphosphinates of Formula III which are used in the preparation of thecompounds of the present invention can be prepared from thecorresponding acids by the methods described by Malatesta and Pizzotti,Chimica e Industria (Milan) 27, 6-10 (1945), and Melnikov and Grapov,Zhur. Vsesoyuz Khim. Obshchestva in D. I. Mendeleeva, 6, No. 1; 119-120(1961). Exemplary of suitable salts are:

potassium dimethylphosphinate potassium diethylphosphinate potassiumdi-n-propylphosphinate potassium diisopropylphosphinate potassiumdi-n-butylphosphinate potassium di-sec-butylphosphinate potassiumdi-t-butylphosphinate potassium dihexylphosphinate potassium diheptylphosphinate potassium didecylphosphinate potassiumphenylmethylphosphinate potassium phenylbutylphosphinate potassiumbenzylphenylphosphinate potassium benzylbutylphosphinate potassiumdiphenylphosphinate potassium (4-chlorophenyl)methylphosphinatepotassium (3-nitrophenyl)methylphosphinate potassium(2-bromophenyl)ethylphosphinate potassium(3-methoxypheny1)propylphosphinate potassium(Z-dimethylaminophenyl)methylphosphinate potassium(4-methylsulfonylphenyl) methylphosphinate potassium3-ethylsulfinylphenyl decylphosphinate potassium bis- [p- (ethylthiophenyl] phosphinate potassium dimethylthiolophosphinate potassiumdiethylthionophosphinate potassium phenylmethylthionothiolophosphinatepotassium (4-chlorobenzyl)methylthiolophosphinate potassiumbis(3,4-dichlorophenyl)phosphinate potassium allylmethylphosphinatepotassium ('2-methyl-4-chlorophenyl) (3-nitrophenyl) phosphinate Themanner in which the compounds of the present invention can be preparedreadily is illustrated in the following examples.

EXAMPLE 1 Preparation of l-methoxyimino-l-methoxy- 2-chloropropane Ether(275 ml.) is added to a 40% aqueous solution of potassium hydroxide ml.)contained in a 500 ml. Erlenmeyer flask and the resulting mixture iscooled in an ice-salt bath to 5 C., with stirring, in the absence oflight. N-nitrosomethylurea (30 grams; 0.29 mol) is added over a periodof about 3 minutes with stirring and continued cooling. The ether phaseis then decanted into a cooled 1 liter flask and a solution ofN-methoxy-a-chloropropionamide (21 grams; 0.16 mol) in ether and ethylalcohol is slowly added, with stirring and cooling, over a period ofabout 2 hours. Stirring and cooling is continued for about 4 hours afterthe addition is completed. The reaction mixture is then allowed to Warmup to room temperature and is dried over magnesium sulfate and filtered.The filtrate is stripped of solvents to yieldl-methoxyimino-lmethoxy-Z-chloropropane.

EXAMPLE 2 Preparation of S-( 1-methyl-2-methoxy-imino-2- methoxyethyldimethylthiolophosphinate A solution of1-methoxyimino-1-methoxy-2-chloropropane (7.6 grams; 0.05 mol) in methylethyl ketone is charged into a glass reaction flask equipped with amechanical stirrer and reflux condenser. Potassiumdimethylthiolophosphinate (6.6 grams; 0.05 mol) is added thereto and thereaction mixture is heated at reflux for a period of about 20 hours withcontinuous stirring. After this time the reaction mixture is cooled andfiltered to remove the potassium chloride that is formed. The filteredsolution is then stripped of solvent and the residue is dissolved inether. The ether solution is washed with water and dried over anhydrousmagnesium sulfate. The dried solution is evaporated under reducedpressure to yield S-(1 methyl-Z-methoxyimino-2-methoxyethyl)dimethylthiolophosphinate.

EXAMPLE 3 Preparation of 1-methoxyimino-1-methoxy-2-phenyl-Z-chloroethaue A newly prepared solution of diazornethane (8.4grams; 0.2 mol) in ether ml.) is placed in a 1 liter glass reactionflask equipped with a magnetic stirrer and is cooled to a temperature ofabout 5 C. A solution of N-methoxy-a-phenyl-a-chloroacetamide (11 grams;0.1 mol) in ether ml.) is then added to the reaction flask, withcontinuous stirring and cooling, over a period of about 1 hour. Afterthe addition is completed, stirring is continued for a period of about 2hours to ensure the completion of the reaction. After this time thereaction mixture is stripped of solvent under reduced pressure to yieldl-methoxy-imino-1-methoxy-2phenyl-2-chlorethane.

5 EXAMPLE 4 Preparation of O-(l-phenyl-2-methoXy-imino-2-methoxyethyl)(4-chlorophenyl)methylphosphinate A solution of1-methoxyimino-1-methoxy-2-phenyl-2- chloroethane (8.3 grams; 0.05 mol)in methyl ethyl ketone (100 m1.) is charged into a glass reaction vesselequipped With a mechanical stirrer and reflux condenser. Potassium(4-chlorophenyl)methylphosphinate (10.7 grams; 0.05 mol) is added to thereaction vessel and the reaction IniX- ture is heated at reflux, withcontinuous stirring, for a period of about 18 hours. After this time thereaction mixture is cooled and filtered to remove the potassium chloridethat is formed. The filtered solution is stripped of solvent and theresidue is dissolved in ether. The ether solution is washed with waterand is dried over anhydrous magnesium sulfate. The dried solution isthen evaporated under reduced pressure to yieldO-(l-phenyl-Z-methoxyimino- Z-methoxyethyl)(4-chlorophenyl)methylphosphinate.

EXAMPLE 5 Preparation of 1-methoxyimino-l-methoxy-Z-(2- methylphenyl-2-chloroethane A newly prepared solution of diazomethane (8.4 grams;0.2 mol) in ether (100 ml.) is placed in a 1 liter glass reaction flaskequipped with a magnetic stirrer and is cooled to a temperature of about5 C. A solution of N-methoxy-u-(2methylphenyl) oz chloroacetamide (12grams; 0.1 mol) in ether (150 ml.) is then added to the reaction flask,with continuous stirring and cooling, over a period of about 1 hour.After the addition is completed, stirring is continued for a period ofabout 1 hour to ensure the completion of the reaction. After this timethe reaction mixture is stripped of solvent under reduced pressure toyield l-methoxyimino-1-methoxy-2-(Z-methylphenyl) -2-chloroeth ane.

EXAMPLE 6 Preparation of S- l- 2-methylphenyl) -2-methoxyimino-2-methoxyethyl] (3,4 dichlorophenyl)methylthiolophosphinate A solution of1-n1ethoxyimino-l-methoxy-2-(2-methylphenyl)-2-chloroethane (9 grams;0.05 mol) in methyl ethyl ketone (100 ml.)) is charged into a glassreaction vessel equipped with a mechanical stirrer and reflux condenser.Potassium (3,4-dichlorophenyl)methylthiolophosphinate (13.2 grams; 0.05mol) is added to the reaction vessel and the reaction mixture is heatedat reflux, with stirring, for a period of about 18 hours, After thistime the reaction mixture is cooled and filtered to remove the potassiumchloride that is formed. The filtered solution is stripped of solventand the resulting residue is redissolved in ether. The ether solution iswashed with water, dried over magnesium sulfate, and is evaporated underreduced pressure to yield S-[ l-(2-methylpheny1)-2- methoxyimino 2methoxyethyl] (3,4-dichlorophenyl) methylthiolophosphinate.

Other compounds within the scope of this invention can be prepared bythe procedures described in the foregoing examples. Presented in thefollowing examples are 8 the essential ingredients required to preparedthe indicated named compounds according to the procedures heretoforedescribed.

EXAMPLE 7 N-methoxy on chloro-n butyramide-i-diazomethane+ potassiumdiethylphosphinate=O-(lethyl-Z-methoxyimino-2-methoxyethyl)diethylphosphinate.

EXAMPLE 8 Nethoxy a(B-dimethylaminophenyl)-ot-chloroacetamide+diazomethane+potassium (3methylsulfonylphenyl)methylphosphinate=0 [l-(3dimethylaminophenyl)-2ethoxyimino-2-methoxyethyl] (3methylsulfonylphenyl methylphosphinate.

EXAMPLE 9 N-n-pentyloxy a (4 iodophenyl)-e-chloroacetamide+diazoethane+potassium (4 methylsulfinylphcnyl)decylthiolophosphinate=S[l (4-iodophenyl)-2-n-pentyloxyimino 2 ethoxyethyl](4-methylsulfinylphenyl)decylthiolophosphinate.

EXAMPLE l0 N-rnethoxy a (3-chlorobenzyl)-rx-chloroacetamide+ diazo noctane-l-potassium diphenylphosphinate=0- [l-(3-chlorobcnzyl) 2methoxyimino-2-octyloxyethyl] diphenylphosphinate.

EXAMPLE ll N-n-propoxy ot-(4-fiuorophenyl)-u-chloroacetamide+ diazo nhexane+potassiurn di-n-pentyithiolophosphinate s-[l (4 fluorophenyl)-2-npropoxyimino-2-nhexyloxyethyl] di-n-pentylthiolophosphinate.

EXAMPLE l2 N-methoxy Or. (4chlorophenethyl)-a-chloroacetamide+diazomethane+potassium(4isopropylthiophenyl)octylthiolophosphinate=S [l (4-chlorophenethyl)-Z-methoxyimino-2-rnethoxyethyl] (4 isopropylthiophenyl) octylthiolophosphinate.

EXAMPLE l3 N-methoxy a(2,4,6-trichlorophenyl)-ot-chloroacetamide+diazomethane+potassium (3phenyl-n-propyl) methylphosphinate=0 [l(2,4,6 trichlorophenyl)-2-methoxyimino 2 methoxyethyl] (3-phenyl-n-propyl) methylphosphinate.

EXAMPLE 14 N-n-butoxy-a-(4 pentenylphenyl) oc chloroacetamide+diazo npropane-i-potassium (4-allylphenyl) (3 bromophenyl)phosphinate=0-[l-(4pentenylphenyl) 2 n-butoxyimino-Z-n-propoxyethyl] (4-allylphenyl)(3-bromophenyl)phosphinate.

EXAMPLE l5 N-methoxy a chlorocaproarnide+diazomethane-ipotassiumdidecylthionophosphinate:0 (l n-butyl-Z- methoxyimino 2methoxyethyl)didecylthionophosphinate.

EXAMPLE l6 N-ethoxy aoenzyl-et-chloroacetarnide+diazomethane-i-potassiurnisopropylmethylphosphinate:O (l-benbyl-2-ethoxyimino 2methoxyethyl)isopropylmethylphosphinate.

Additional compounds within the scope of this invention can be preparedby the procedures of the foregoing examples. Exemplary of such compoundsare O-( 1-methyl-2-methoxyimino-Z-methoxyethyl) dimethylphosphinate,

O-(l-allyl-2-methoxyimino-Z-methoxyethyl) isopropylphenylphosphinate,

O-( 1-allyloxy-2-methoxyimino-2-methoxyethyl) (3-methylphenyl)methylphosphinate,

O-(1-pentenyloxy-2-ethoxyimino-2-methoxyethyl) benzylphenylphosphinate,

O-( 1-pentenylthio-2-t-butylimino-2-methoxyethyl) (3-bromophenyl)benzylphosphinate,

O- 1-decylthio-2-methoxyimino-Z-ethoxyethyl) (4-tbutylphenyl)(4-chlorophenyl)phosphinate,

S-[ 1- 3-chloro-4-nitrophenyl -2-methoxyimino-2-methoxyethyl](4-pentylsulfinylphenyl) (Z-methoxyphenyl thiolophosphinate,

O[ 1- (4-butylthiophenyl -2-methoxyimino-2-methoxyethyl](Z-pentyloxyphenyl) (3,4-diiodobenzyl) phosphinate,

O-[ l- (2,6-dimethoxyphenyl -2-methoxyimino-2-methoxyethyl] [3-3,4-dichlorophenyi)-propyl] (3- nitrobenzyl thionophosphinate,

O- l-phenyl-2-methoxyimino-2-n-butoxyethyl) (4-dihexylaminophenyl)(3,4-dichlorophenyl phosphinate,

S-( l-octyl-2-ethoxyirnino-Z-methoxyethyl) (3 -decyloxyphenyl)4-n-butylsulfinylphenyl) thiolophosphinate,

S- l-hexyloxy-Z-methxyimino-2-rnethoxyethyl) [3- (4- methylphenyl-propyl] (4-bromobenzyl thiolothionophosphinate,

S- l-(3-phenylpropyl)-2-methoxyimino-2-methoxyethyl]dimethylthiolophosphinate,

S-[1-(3-hexenylphenyl)-2-methoxyimino-2-methoxyethyl](4-isopropylsulfonylphenyl) (3-methylthiophenyl) thiolophosphinate, andthe like.

For practical use as insecticides or acaricides, the compounds of thisinvention are generally incorporated into insecticidal or acaricidalcompositions which comprise an inert carrier and an insecticidally oracaricidally toxic amount of such a compound. Such insecticidal oracaricidal compositions, which can also be called formulations, enablethe active compound to be applied conveniently to the site of the insector acarid infestation in any desired quantity. These compositions can besolids such as dusts, granules or wettable powders; or they can beliquids such as solutions, aerosols or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the tales, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water and/or oil to anydesired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufiiciently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofinsecticides or acaricides can be dispersed under superatmosphericpressure as aerosols. However preferred liquid insecticidal oracaricidal compositions are emulsifiable concentrates, which comprise anactive compound according to this invention and as the inert carrier, asolvent and an emulsifier. Such emulsifiable concentrates can beextended with water and/or oil to any desired concentration of activecompound for application as sprays to the site of the insect or acaridinfestation. The emulsifiers most commonly used in these concentratesare nonionic or mixtures of nonionic with anionic surface-active agents.

A typical insecticidal or acaricidal composition according to thisinvention is illustrated by the following example, in which thequantities are in parts by weight.

EXAMPLE 19 Preparation of a dust Product of Example 2 l0 Powdered talcThe above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, free-flowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the insect or acarid infestation.

The compounds of this invention can be applied as insecticides oracaricides in any manner recognized by the art. One method fordestroying insects or acarids comprises applying to the locus of theinsect or acarid infestation, an insecticidal or acaricidal compositioncomprising an inert carrier and, as an essential active ingredient, in aquantity which is toxic to said insects or acarids, a compound of thepresent invention. The concentration of the new compounds of thisinvetnion in the insecticidal or acaricidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the insecticidal or acaricidal compositions willcomprise from about 0.05 to about percent by weight of the activecompounds of this invention. In a preferred embodiment of thisinvention, the insecticidal or acaricidal compositions will comprisefrom about 5 to 75 percent by weight of the active compound. Thecompositions can also comprise such additional substances as otherpesticides, stabilizers, spreaders, deactivators, adhesives, stickers,fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other insecticides or acaricides in the compositions heretoforedescribed. These other insecticides or acaricides can comprise fromabout 5% to about 95% of the active ingredients in the compositions. Useof the combinations of these other insecticides or acaricides with thecompounds of the present invention provide insecticidal and/ oracaricidal compositions which are more effective in controlling insectsor acarids and often provide results unattainable with separatecompositions of the individual compounds. The other insecticides oracaricides with which the compounds of this invention can be used in theinsecticidal or acaricidal compositions to control insects or acaridsinclude halogenated compounds such as DDT, methoxychlor, TDE, lindane,chlordane, isobenzan, aldrin, dieldrin, heptachlor, endrin, mirex,endosulfon, dicofol, and the like; organic phosphorus compounds such asTEPP, schradan, ethion, parathion, methyl parathion, EPN, demeton,carbopenothion, phorate, zinophos, diazinon, malathion, rnevinphos,dimethoate, DBD, ronnel, oxydemeton-methyl, dicapthon, chlorothion,phosphamidon, naled, fenthion, trichlorofon, DDVP, and the like; organicnitrogen compounds such as dinitro-o-cresol, dinitrocyclohexylphenol,DNB, DNP, binapacril, azobenzene, and the like; organic carbamatecompounds such as carbaryl, ortho 5353, and the like; organic sulfurcompounds such as phenothiazine, phenoxathin, lauryl thiocyanate,[bis(2-thiocyanoethyl)ether], isobornyl thiocyanoacetate, and the like;as well as such substances usually referred to as fumigants, as hydrogencyanide, carbon tetrachloride, calcium cyanide, carbon disulfide,ethylene dichloride, propylene dichloride, ethylene dibromide, ethyleneoxide, methyl bromide, paradichlorobenzene, and the like.

The compounds of the present invention can also be combined withfungicidal and nematocidal chemical compounds to form pesticidalcompositions useful for the control of fungi and in some cases soilnematodes as well as insects or acarids. Typical examples of suchfungicidal chemical compounds are ferbam, nabam, zineb, ziram, thiram,chloranil, dichlone, glyodin, cycloheximide, dinocap, maneb, captan,dodine, PCNB, p -d1- methylaminobenzenediazo sodium sulfonate, and thelike; while examples of nematocidal compounds are chloropicrin,0,0-diethyl O(2,4-dichlorophenyl) phosphorothioate,tetrachlorothiophene, dazomet, dibromochloropropane, and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects or acarids. Insecticides or acaricides which are tobe used as stomach poisons or protective materials can be applied to thesurface on which the insects or acarids feed or travel. Insecticides oracaricides which are to be used as contact poisons or eradicants can beapplied directly to the body of the insect or acarid, as a residualtreatment to the surface on which the insect or acarid may walk orcrawl, or as a fumigant treatment of the air which the insect or acaridbreathes. In some cases, the compounds applied to the soil or plantsurfaces are taken up by the plant, and the insects or acarids arepoisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.Among the insects which can be effectively controlled by the compoundsof the present invention are the chewing insects, such as the Mexicanbean beetle and the southern armyworm; the piercing-sucking insects,such as the pea aphid, the cereal leaf beetle, the housefly, the grapeleafhopper, the chinch bug, the lygus bug, the oyster shell scale, theCalifornia red scale, the Florida red scale, the soft scale andmosquitoes; the internal feeders, including borers, such as the Europeancorn borer, the peach twig borer and the corn earworm, worms or weevils,such as the codling moth, the alfalfa weevil, the cotton boll weevil,the pink boll worm, the plum curculio, the red banded leaf roller, themelonworm, the cabbage looper and the apple maggot, leaf miners, such asthe apple leaf miner, the birch leaf miner and the beet leaf miner, andgall insects, such as the wheat joint worm and the grape phylloxera.Insects which attack below the surface of the ground are classified assubterranean insects and include such destructive pests as the woolyapple aphid, the Japanese beetle, the onion maggot and the cornroot-Worm.

Mites and ticks are not true insects. Many economically importantspecies of mites and ticks can be controlled by the compounds of thepresent invention, such as the red spider mite, the two-spotted mite,the strawberry spider mite, the citrus rust mite, the cattle tick, thepoultry mite, the citrus red mite and the European red mite. Chemicalsuseful for the control of mites are often called miticides, while thoseuseful for the control of both mites and ticks are known specifically asacaricides.

The quantity of active compound of this invention to be used for insector acarid control will depend on a variety of factors, such as thespecific insect involved, intensity of the infestation, weather, type ofenvironment, type of formulation, and the like. For example, theapplication of only one or two ounces of active chemical per acre may beadequate. for control of a light infestation of an insect or acaridunder conditions unfavorable for its feeding, while a pound or more ofactive compound per acre may be required for the control of a heavyinfestation of insects or acarids under conditions favorable to theirdevelopment.

The insecticidal utility of the compounds of the. present invention canbe demonstrated, for example, by experiments carried out for the controlof insects by feeding. In one experiment, for the systemic control ofthe pea aphid (Acyrthosiphon pisum), 5 day old Laxton pea plants arewatered with 30 ml. of an aqueous emulsion of an acetone solution of thetest compound and are thereafter infested with ten newly molted adultpea aphids. The infested plants are then placed in a holding chamber at65 F. for a period of 48 hours and are supplied with Water and light asrequired. After the 48 hours the mortality of the pea aphids isdetermined and rated on a percent basis in comparison to an untreatedcontrol. The results of this experiment indicate the high degree ofactivity possessed by the compounds of this invention.

The insecticidal utility of the compounds of this invention as contactpoisons can be demonstrated, for example, in an experiment carried outfor the control of the housefly (Musca domestica). In this experimenteach of fifty flies is contacted with the test compounds, formulated asan aqueous emulsion of an acetone solution, by applying the formulationto the dorsum of its thorax. The flies are then placed in a wire meshcage where they are supplied with sugar syrup. After the end of a 24hour period the mortality of the flies is observed and is rated incomparison to untreated controls. The results of this experimentindicate the high degree of activity possessed by the compounds of thisinvention.

The acaricidal utility of the compounds of the present invention can bedemonstrated, for example, by experiments carried out for the control ofthe two-spotted spider mite (Tetranychus urticae). In one suchexperiment, wherein the systemic activity is demonstrated, 5 day oldHenderson bush lima bean plants are each watered with 30 ml. of aformulation containing the test compounds at a concentration of 3500parts per million. After a period of 48 hours the plants are infestedwith two-spotted spider mites and are placed in a holding room andsupplied with water and light as required. After a period of 5 days themortality of the mites is determined and rated on a percent basis incomparison to untreated controls. The results of this experimentindicate the high degree of acaricidal activity possessed by thecompounds of this invention.

We claim: l. A compound of the formula X 0-R Y I X -CH( J=NOR wherein Yand Y are independently selected from the group consisting of loweralkyl, lower alkenyl and wherein Z is selected from the group consistingof lower alkyl, lower alkenyl, lower alkoxy, lower alkylthio, halogen,nitro, diloweralkylamino, lower alkylsulfoxide and lower alkylsulfone, mis an integer from 0 to 3, and n is an integer from 0 to 3; Q isselected from the group consisting of lower alkyl, lower :alkenyl, loweralkoxy, lower alkylthio and wherein B is selected from the groupconsisting of lower alkyl, lower alkenyl, lower alkoxy, lower alkylthio,halogen, nitro, diloweralkylamino, lower alkylsulfoxide and loweralkylsulfone, p is an integer from 0 to 5, A is selected from the groupconsisting of oxygen, sulfur, lower alkylene, lower alkyleneoxy andlower alkylenethio, and q is an integer from 0 to l; X and X areindependently selected from the group consisting of oxygen and sulfur;and R and R are alkyl.

2. The compound of claim 1, S-(l-methyl-Z-methoxyimino-2-methoxyethyl)dimethylthiolophosphinate.

3. The compound of claim 1, O-(l-ethyl-Z-methoxy- No references cited.imino-Z-methoxyethyl) phenylmethylphosphinate.

4. The compound of claim 1, O-(l-phenyl-Z-methoxy- CHARLES B. PARKER,Prlmary Examiner imino 2 methoxyethyl) (4-ch1oropheny1)methylphos- SUTTOAssistantEXaminer phinate. 5 i

5. The compound of claim 1, S-[I-(Z-methylphenyD- Us CLXR 2methoxyimino-2-methoxyethy1] (3,4-dichloropheny1)-methylthiolophosphinate. 26O 453R 978; 424-211 6. The compound of claim1, O-[1-(4-ch1oropheny1)- Z-methoxyimino-2-methoxyethyl]diethylphosphinate. 1O

$223? UNITED S'LAIES PA'IENT OFFICE CERTIFICATE OF CORRECTION Patent5,597,5 Dated August 5, 97

Invcnt0r(s) Sidney B. Richter and Ephraim H. 'Kaplan It is: certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In cloumn 2 delete line 47 and in place thereof insert The compounds ofthis invention can be readily pre- In column 7, line 1 for "byl" read--zyl--.

Signed and sealed this 28th day of March 1972.

(SEAL) Attest:

EDWARD M.F'LETCHER,JR. ROBERT GOTTSCHALK Attesting Officer ICommissioner of Patents

